Azo dyestuffs and process of making same



Patented Aug. 18, 1931 UNITED STATES BEBTZRAM MAYER, or BASEL, AND 'JosnrH 'G-RIMMER, on nnunwnnr; armament;

PATENT 0mm SWITZERLAND, ASSIGNORS T0 SOCIETY OF CHEMICAL INDUSTRY IN BASEE, (3F

BASEL, SWITZERLAND AZO DYEST'UFFS PROCESS OF MAKING SAME No Drawing. Application filed October 11, 1928, Serial No. 311,960, and in Switzerland. October 31, 1927.

The present invention relates to the manufacture of azo-dyestuffs. It comprises the process of making the new dyestuffs, the dye stufls themselves, and the material that has been dyed with the new products.

' It has been found that direct-dyeing cotamino-group, then diazotizing the disazodyestutf thus produced of the general formula I R VN=N- N=NR NH wherein R R and R have the significations hereinafter given, and coupling in acid, neutral or alkaline medium with 1-amino-5-hydroxynaphthalene-7-sulfonic acid.

The dyestuffs thus made are dark powders, corresponding with the general formula wherein R R and R signify benzene or naphthalene nuclei which contain no free hydroxy-groups and of which at least two contain sulfo-groups, and R means the residue of lsamino-5-hydroxynaphthalene-7- sulfonicacid. They dissolve in water containing sodium carbonate and concentrated sulfuric \acid to blue grey to green grey solutions-and dye cotton in neutral or feebly alkaline baths very uniform grey to blue grey and green grey tints of good fastness to light. This is also the case with the dyestuffs in which the end component .has been coupled in a medium the pH of which lies between 1.5 and 8.4. Such a medium contains inter 'alia aik-ali bicarbonate or an alltalivacetate or phosphate as an acid binding agent. The following examples illustrate the invention, the iparts being by weight Example 1 i 9.3 parts of aniline are diazotiZed asnsual "and coupled with 22.3 parts of Cleves acid. The monoazo-dyestuil is diazotized in known manner by means of nitrite and hydrochloric acid and the .di'aZo-compound thus produced is coupled with 22.3 parts of Gleves aoijd. When-coupling is complete the disazo-riyestuflf is salted out with common salt and liltered. After suspending :the filter cakein water there is added thenecessary ouai 'ty of hydrochloric acid andthe mixture isdi'aao tizedi n usual manner by adding the calculated quantity of nitrite at 0C. Ass-con the dia-zotization iscoinplete, the diazo-compound is run, while stirring, into a solution, alkaline with sodium carbonate, of :24- parts of l-amino-5hydroxynaphthalene-fi sulfoni-c acid. The combination is at once finished and the trisazo-dyestufi is salted out, filtered and dried. a

The product, corresponding very probably with the formula NH-g soari- "wherein the one of the ws and the one'ofthe ys stands fora hydrogen atom and the other w and the-other 3 foran SO H group, is a black powder which dissolves .in' water, *containing sodium carbonate, to 'a' green grey solution. The solution concentrated suliuric acid is greenish blue grey. Theproduct dyes cotton green grey. Sin'lilar pro'dnets are obtained when for the aniline is substituted atoluidine or a sulfonic'a'cidot aniline or of toluidine or para-aminoacetanilide, and for the -Cleveacid a-naphthylami'ne or cresidine. As initial component may also be 4:8-disulfonate are diazotized in the usual manner by means of sodlum nitrite and O hydrochloric acid and coupled with 14.5

another initial component of the naphthalene series, such as ocor ,B-naphthylamine or a sulfonic acid thereof, and for the middle components named others may be substituted, care being taken that the dyestufi pro- Color of the Color of the Color-of Color of 3rd com- 4th comsolution alkasolution in con- 1st component 2nd component penent ponent agg line with socentrated g ag g l p v diurn carbonate H Metanilie acid Cleve-acid Cleve-acid 1-amino-5- black blue grey greenish blue pure grey hydroxynaphgrey t h a 1 en e -7- sulfonic acid (alkaline) black greenish hluegreenish blue greenish (acid) grey grey grey Z-aminonaphthalenea-naphthylamine black blue grey greenish blue pure blue 4:8-disulfonie acid (alkaline) grey grey black greenish blue greenish blue green grey (acid) grey grey Aniline Cleve-acid "i black green grey greenish blue green grey 1 (alkaline) grey black greenish blue greenish blue green grey (acid) grey grey V Metamlic acid rx-naphthylamine 1k If black blue grey green grey v ure grey a a me black blue grey greenish blue green grey (acid) grey Cleve-acid Cleve-acid black blue grey greenish blue pure blue (alkaline) grey grey I black greenish blue greenish blue green grey (acid) grey grey parts of a-naphthylamine. The d yestufi" produced is isolated, further diazotized and coupled with 22.3 parts of Cleve-acid. After complete combination the disazo-dyestuff is further diazotized and then the diaZo-con1- pound is added to a solution of 24 parts of 1amino-5-hydroxynaphthalene-7-sulfonic acid which has been converted into sodium salt by alkali and mixed withso much sodium acetate that the reaction is acid to litmus after the addition of the diazo-compound. The coupling is complete in a short time. The trisazo-dyestufl' is changed into its sodium salt, saltedout, filtered and dried. The product, corresponding very probably with the formula SOJH What we claim is 1. The manufacture of direct-dyeing cotton dyestuffs diazotizing a disaZo-dyestuif of the general formula in which R R and R signify benzene or naphthalene nuclei which contain no. hy-

droxy-groups, and of whichat least two contain sulfo-groups, and coupling the diazocompound thus formed with the 1-amino-5- hydroxynaphthalene-T-sulfonic acid.

2. The manufacture of direct-dyeing cotton dyestuffs by diazotizing a disazo-dyestufi' of the general formula in which R R and R signify naphthalene nuclei which contain no hydroXy-groups, and in which R and R contain at least one sulfo-group, and coupling the diazo-com- 5 pound thus formed with the 1-amino-5-hydroxynaphthalene-7-sulfonic acid in such a medium the pH of which lies between 1.5 and 8A.

4. As new products the azo-dyestuifs of the 10 general formula whereinR ,R and R signify benzene or naphthalene nuclei which contain no free hydroXygroups and of which at least two contain sulfo-groups, and R means the residue of 1-amino-5-hydroxynaphthalene-7-sulfonio acid, which products form dark powders, dissolving in water containin sodium carbonate and in concentrated sulfuric acid to bluegrey to green-grey solutions, and dyeing cotton in neutral or feebly alkaline baths very uniform grey to blue-grey and green-grey tints of good fastness to light.

5. As new products the azo-dyestuffs of the general formula wherein R R and R signify benzene or naphthalene nuclei which contain no hydroxy-group, R and R containing at least one sulfo-group, and wherein R signifies the residue of 1-amino-5-hydroxynaphthalone-7- sulfonic acid, which products form dark powders, dissolving in water containing sodium carbonate and in concentrated sulfuric acid to blue-grey to green-grey solutions, and dyeing cotton in neutral or feebly alkaline baths very uniform grey to blue-grey and greengrey tints of good fastness to light.

6. As new products the azo-dyestulfs of the general formula wherein R R and R signify benzene or naphthalene nuclei which contain no hydroXy-group, R and R containing at least one sulfo-group, and wherein R signifies the residue of 1-amino-5-hydroxynaphthalene- 7 -sulfonic acid which is linked with the amgroup in position 4, which products form dark powders, dissolving in water containing sodium carbonate and in concentrated sulfuric acid to blue-grey to green-grey solutions, and dyeing cotton in neutral or feebly alkaline baths very uniform grey to bluegrey and green-grey tints of good fastness to light.

In witness whereof we have hereunto 6O signed our names this 29th day of September,

BERTRAM MAYER. JOSEPH GRIMMER. 

